This invention relates to protein macromolecular dyes, especially to the protein macromolecular dyes which are prepared by reacting protein macromolecules with the reactive dyes.
There were descriptions related to polymeric dyes in the prior art. In European patent publication No. 0 205 290 (1986), colored polymer was prepared by the copolymerization of the azo dyes containing unsaturated olefin. And U.S. Pat. No. 4,477,635 described the preparation of polymeric triarylmethane dye by polycondensation. The defect of preparing polymeric dye by copolymerization or polycondensation was that dyes and intermediates in copolymerization and polycondensation should not contain the inhibited groups such as nitro and amino groups. But these inhibited groups were necessary auxochromo groups for bright dyes. Therefore, the conversion of the dyes and the content of the parent dyes in the polymeric dyes were low when the conventional dyes were used in the polymerization for preparing polymeric dyes.
In U.S. Pat. No. 4,546,161 (1985) an affinity chromatography carrier for protein separation was described. Polymer and copolymer of agarose, dextrose, dextran and acrylamide was used as the support matrix of the carrier bearing mono- or dichloro triazine dyes which were added by chemical reaction. The combination amount of the dye combined onto the macromolecule was lower than 10% in the carrier.
As the content of the parent dyes on the support matrix in the prior macromolecule is low, the present invention suggests protein macromolecular dyes with high content of the parent dyes. It is synthesized by the reaction of the amino groups of protein macromolecules used as polymeric support matrix with parent dyes.
So far, there is no report about protein macromolecular dyes in publications.
The object of the present invention is to provide protein macromolecular dyes synthesized by the reaction of protein macromolecules with dyes, and to overcome the low binding amount of the parent dyes in macromolecular support matrix of prior macromolecular dyes. This kind of protein macromolecular dyes has good properties such as color brightness, coloring ability, fastness, anti-mobility, compatibility and environmental safety in dyeing protein materials such as leather, wool and silk.
The present invention provides protein macromolecular dyes having the formula:
A(B)bxe2x80x83xe2x80x83(1)
wherein A are protein macromolecules, B are dyes which can react with the amino groups of the protein macromolecules, b are integers between 1xcx9c2500.
The present invention provides protein macromolecular dyes wherein dyes B are azo dyes, which can react with the amino groups of the protein macromolecules A.
The present invention provides protein macromolecular dyes wherein dyes B are azo metal complex dyes, which can react with the amino groups of the protein macromolecules A.
The present invention provides protein macromolecular dyes wherein dyes B are anthraquinone dyes, which can react with the amino groups of the protein macromolecules A.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A are natural protein macromolecules with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the azo dyes are natural protein macromolecules with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the azo metal complex dyes are natural protein macromolecules with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the anthraquinone dyes are natural protein macromolecules with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecules A which can react with the dye B is casein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the dye B is gelatin with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the dye B is fur-protein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo dye B is casein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo dye B is gelatin with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo dye B is fur-protein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo metal complex dye B is casein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo metal complex dye B is gelatin with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the azo metal complex dye B is fur-protein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the anthraquinone dye B is casein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the anthraquinone dye B is gelatin with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the natural protein macromolecule A which can react with the anthraquinone dye B is fur-protein with 1000xcx9c450000 molecular weight.
The present invention provides protein macromolecular dyes wherein the protein macromolecule A for preparing protein macromolecular dyes are expressed as follows:
Axe2x80x2(D)dxe2x80x83xe2x80x83(2)
wherein Axe2x80x2 are the modified protein macromolecules derived from the protein macromolecules A of which 0.1xcx9c95% amino groups are substituted by the dye, d are integers between 1xcx9c2400, D are single or mixed groups as follows: 
wherein R1 is xe2x80x94H or xe2x80x94CH3; n are integers between 1xcx9c1000; R2 is xe2x80x94COOH, xe2x80x94CONH2, xe2x80x94CN, xe2x80x94COOCH3, xe2x80x94COOC2H5, xe2x80x94COOC3H7, xe2x80x94COOC4H9, xe2x80x94Cl, xe2x80x94CHO, xe2x80x94COOC2H4OH, or 
wherein m are integers between 1xcx9c200; R1 is xe2x80x94H, 
R2 is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5; 
wherein m1 are integers between 1xcx9c300; R1 is xe2x80x94H, or 
R2 is H, xe2x80x94CH3, or xe2x80x94C2H5.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the azo dyes are expressed as follows:
Axe2x80x2(D)dxe2x80x83xe2x80x83(6)
wherein Axe2x80x2 are the modified protein macromolecules derived from the protein macromolecules A of which 0.1xcx9c95% amino groups are substituted by the dye, d are integers between 1xcx9c2400, D are single or mixed groups as follows: 
wherein R1 is xe2x80x94H or xe2x80x94CH3; n are integers between 1xcx9c1000; R2 is xe2x80x94COOH, xe2x80x94CONH2, xe2x80x94CN, xe2x80x94COOCH3, xe2x80x94COOC2H5, xe2x80x94COOC3H7, xe2x80x94COOC4H9, xe2x80x94Cl, xe2x80x94CHO, xe2x80x94COOC2H4OH or 
wherein m are integers between 1xcx9c200; R1 is xe2x80x94H, 
R2 is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5; 
wherein m1 are integers between 1xcx9c300; R1 is xe2x80x94H, 
wherein R2 is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the azo metal complex dyes are expressed as follows:
Axe2x80x2(D)dxe2x80x83xe2x80x83(10)
wherein Axe2x80x2 are the modified protein macromolecules derived from the protein macromolecules A of which 0.1xcx9c95% amino groups are substituted by the dye, d are integers between 1xcx9c2400, D are single or mixed groups as follows: 
wherein R1 is xe2x80x94H or xe2x80x94CH3; n are integers between 1xcx9c1000; R2 is xe2x80x94COOH, xe2x80x94CONH2, xe2x80x94CN, xe2x80x94COOCH3, xe2x80x94COOC2H5, xe2x80x94COOC3H7, xe2x80x94COOC4H9, xe2x80x94Cl, xe2x80x94CHO, xe2x80x94COOC2H4OH or 
wherein m are integers between 1xcx9c200; R1 is xe2x80x94H, 
R2 is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5; 
wherein m1 are integers between 1xcx9c300; R1 is xe2x80x94H, or 
R2 is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5.
The present invention provides protein macromolecular dyes wherein the protein macromolecules A which can react with the anthraquinone dyes are expressed as follows:
Axe2x80x2(D)dxe2x80x83xe2x80x83(14)
wherein Axe2x80x2 are the modified protein macromolecules derived from the protein macromolecules A of which 0.1xcx9c95% amino groups are substituted by the dye, d are integers between 1xcx9c2400, D are single or mixed groups as follows: 
wherein R1 is xe2x80x94H or xe2x80x94CH3; n are integers between 1xcx9c1000; R2 is xe2x80x94COOH, xe2x80x94CONH2, xe2x80x94CN, xe2x80x94COOCH3, xe2x80x94COOC2H5, xe2x80x94COOC3H7, xe2x80x94COOC4H9, xe2x80x94Cl, xe2x80x94CHO, xe2x80x94COOC2H4OH, or 
wherein m are integers between 1xcx9c200; R1 is xe2x80x94H, 
wherein R2 is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5; 
wherein m1 are integers between 1xcx9c300; R1 is xe2x80x94H, or 
wherein R2 is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (6) is the azo dye which has the structure 
wherein R1, R4 and R8 each represents xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94OH, xe2x80x94COOX or xe2x80x94SO3X respectively; R5 is xe2x80x94H, xe2x80x94CH3, xe2x80x94COOX, xe2x80x94SO3X, or xe2x80x94SO2NH2, 
R2, R3, R6 and R7 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94OCH3, xe2x80x94NO2, xe2x80x94SO2NHR, 
xe2x80x94SO2CH2CH2Y3, xe2x80x94SO2NHCH2CH2Y3, 
xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6;
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, xe2x80x94N(C2H4OH)2, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (6) is the azo dye which has the structure 
wherein R4, R7 and R8 each represents xe2x80x94H, xe2x80x94CH3, xe2x80x94OH, xe2x80x94OCH3, xe2x80x94NO2, xe2x80x94SO3X, or xe2x80x94COOX respectively; R1, R2, R3, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94CH3, xe2x80x94OR, xe2x80x94SO3X, xe2x80x94Cl, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NO2, xe2x80x94N(R)2, xe2x80x94NHCONH2, xe2x80x94NHCOCH3, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, xe2x80x94N(C2H4OH)2, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (6) is the azo dye which has the structure 
wherein R3 is xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94OH, xe2x80x94COOX, xe2x80x94SO3X, xe2x80x94SO2NH2 or xe2x80x94NHCOCH3; R1, R2 and R4 each represents respectively xe2x80x94H, 
xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OR, xe2x80x94NO2, xe2x80x94N(R)2, xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, xe2x80x94N(C2H4OH)2, xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (10) is the azo metal complex dye which has the structure 
wherein Me is Cu, Co, Ni or Cr; R1, R2, R3, R4, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94CH2SO3X, xe2x80x94NO2, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94NH2, xe2x80x94N(CH3)2, xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94N(R)2, xe2x80x94NHCH2SO3X, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, xe2x80x94N(C2H4OH)2, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X, xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (10) is the azo metal complex dye which has the structure 
wherein Me is Cu, Co, Ni or Cr; R1, R2, R3, R4, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NH2, xe2x80x94N(CH3)2, 
xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, xe2x80x94SO2NHCH2CH2Y3, 
xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (10) is the azo metal complex dye which has the structure 
wherein Me is Cu, Co, Ni or Cr; R1, R2, R3, R4, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NH2, xe2x80x94N(CH3)2, 
xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, xe2x80x94SO2NHCH2CH2Y3, 
xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (10) is the azo metal complex dye which has the structure 
wherein Me is Cu, Co, Ni or Cr; R1, R2, R3, R4, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NH2, xe2x80x94N(CH3)2, 
xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(C2H4OH)2, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The present invention provides protein macromolecular dyes wherein dye B which can react with the protein macromolecules including natural protein macromolecules such as casein, gelatin, fur-protein, and the modified protein macromolecules according to formula (2) and (14) is the anthraquinone dye which has the structure 
wherein m or n is 0 or 1 respectively; L is 0, 1, 2, or 3; J is xe2x80x94CH3, xe2x80x94Cl, xe2x80x94SO3X; G is 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94N(R)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
An embodiment of the present invention is described in detail as follows:
The present invention provides a synthesis process for protein macromolecular dyes in which protein macromolecules consisting of amino acids or the modified protein macromolecules is reacted with azo dyes, azo metal complex dyes, anthraquinone dyes at pH ranging from 2-12, the former is used as macromolecular backbone, the latter bears the reactive groups such as halotriazinyl, halopyrimidinyl, ethylsulphonyl, N-ethyl aminosulfonyl, N-ethyl sulfonylamino, (N-vinylcarbonyl)amino, propionamido and their derivatives.
The structure of the protein macromolecular dyes may be expressed as follows: 
Wherein - - - - is the protein macromolecules or modified protein macromolecules as the polymeric support matrix; L is the linking group including triazinyl, pyrimidinyl, ethylsulfonyl, N-ethyl aminosulfonyl, N-ethylsulfonylamino, (N-vinylcarbonyl)amino, propionamido and their derivatives; D is a parent dye including the azo dye, azo metal complex dye and anthraquinone dye.
There are abundant reactive amino groups in the protein macromolecules including the natural protein macromolecules consisting of amino acids and the modified protein macromolecules. The protein macromolecular dyes can be prepared by the reaction between the amino groups of the protein macromolecules and the reactive groups of the dyes. The processes are completed according to the equations as follows:
(1) The dyes with halotriazinyl reactive groups or their derivatives, react with the amino groups of the protein macromolecules or modified protein macromolecules on the basis of a nucleophilic substitution reaction: 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; D is the parent dye including azo dyes, azo metal complex dyes and anthraquinone dyes.
(2) The dyes with halopyrimidinyl reactive groups or their derivatives, react with the amino groups of the protein macromolecules and modified protein macromolecules on the basis of a nucleophilic substitution reaction: 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94SO2R, xe2x80x94NHCH2SO3X, xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; D is the parent dye including azo dyes, azo metal complex dyes and anthraquinone dyes.
(3) The dyes with ethylsulfonyl, N-ethyl aminosulfonyl, N-ethylsulfonylamino reactive groups or their derivatives, react with the amino groups of the protein macromolecules and modified protein macromolecules on the basis of elimination-addition reaction:
a. The elimination reactions are completed respectively as follows: 
b. The additions with the amino groups are completed respectively as follows: 
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; D is the parent dye including azo dyes, azo metal complex dyes and anthraquinone dyes.
(4) The dyes with (N-vinylcarbonyl)amino or their derivatives, react with the amino groups of the protein macromolecules and modified protein macromolecules on the basis of a reaction as follows:
The molecular formula of the dye containing (N-vinylcarbonyl)amino or its derivatives is expressed as follows:
Dxe2x80x94NHCOxe2x80x94CY4xe2x95x90CHY5
a. when Y4 is xe2x80x94H; Y5 is xe2x80x94H or xe2x80x94Cl, the nucleophilic addition reactions are completed as follows:
Dxe2x80x94NHCOxe2x80x94CHxe2x95x90CH2+NHxe2x80x94xe2x86x92Dxe2x80x94NHCOCH2CH2xe2x80x94NHxe2x80x94xe2x80x83xe2x80x83(E9)
Dxe2x80x94NHxe2x80x94COxe2x80x94CHxe2x95x90CHCl+NHxe2x80x94xe2x86x92Dxe2x80x94NHCOCH2CHClxe2x80x94NHxe2x80x94xe2x80x83xe2x80x83(E10)
b. when Y4 is xe2x80x94Br; Y5 is xe2x80x94H, the addition-substitution reactions are completed as follows: 
c. when Y4 and Y5 both represent xe2x80x94Br, the elimination-addition-substitution reaction is completed as follows: 
wherein D are the parent dyes including the azo dyes, azo metal complex dyes and anthraquinone dyes.
(5) The dyes with propionamido and its derivatives, react with the amino groups of the protein macromolecules or modified protein macromolecules on the basis of the reaction as follows:
The molecular formula of the dye containing propionamido or its derivatives is expressed as follows:
Dxe2x80x94NHCOCHY4CH2Y6
a. When Y4 is xe2x80x94H, Y6 is xe2x80x94OSO3X, the elimination-addition reactions are completed as follows: 
b. When Y4 and Y6 both represent xe2x80x94Br, the elimination-addition-substitution reactions are completed as follows: 
wherein D are the parent dyes including the azo dyes, azo metal complex dyes and anthraquinone dyes.
The present invention provides the natural protein macromolecules as the polymeric support matrix. The natural protein macromolecules consisting of the amino acids include gelatin prepared by the bone, skin, tendon, horn core of big mammals; casein prepared by the milk of big mammals and fur-protein prepared by fur-fabric of mammals.
The reactive groups of the dyes reacting with the amino groups of the protein macromolecules have the structure 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K. 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, or 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
(3) xe2x80x94SO2CH2CH2Y3xe2x80x83xe2x80x83(F3)
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
(4) xe2x80x94SO2NHCH2CH2Y3xe2x80x83xe2x80x83(F4)
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
xe2x80x83(5) xe2x80x94Nxe2x80x94SO2CH2CH2Y3xe2x80x83xe2x80x83(F5)
R
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; R is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
(6) xe2x80x94NHCOCY4xe2x95x90CHY5xe2x80x83xe2x80x83(F6)
wherein Y4 is xe2x80x94H, or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl, or xe2x80x94Br.
(7) xe2x80x94NHCOCHY4CH2Y6xe2x80x83xe2x80x83(F7)
wherein Y4 is xe2x80x94H, or xe2x80x94Br; Y6 is xe2x80x94Br, or xe2x80x94OSO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
The present invention provides the modified protein macromolecules used as the polymeric support matrix. The modified protein macromolecules have the structure
Axe2x80x2(D)d
wherein Axe2x80x2 are the modified protein macromolecules derived from the protein macromolecules A of which 0.1xcx9c95% amino groups are substituted by the dyes, d are integers between 1xcx9c2400, D are single or mixed groups as follows: 
wherein R1 is xe2x80x94H or xe2x80x94CH3; n are integers between 1xcx9c1000; R2 is xe2x80x94COOH, xe2x80x94CONH2, xe2x80x94CN, xe2x80x94COOCH3, xe2x80x94COOC2H5, xe2x80x94COOC3H7, xe2x80x94COOC4H9, xe2x80x94Cl, xe2x80x94CHO, xe2x80x94COOC2H4OH, or 
wherein m are integers between 1xcx9c200; R1 is xe2x80x94H, 
R2 is xe2x80x94H, xe2x80x94CH3, xe2x80x94C2H5; 
wherein m1 are integers between 1xcx9c300; R1 is xe2x80x94H, or 
R2 is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5.
The modified protein macromolecules are prepared by solution polymerization, emulsion polymerization, suspension polymerization or polycondensation between monomers and the natural protein macromolecules such as casein, gelatin and fur-protein. The monomers may be a single or mixed compounds of acrylic acid, methacrylic acid, acrylamide, methylacrylamide, acrylonitrile, methylacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, methyl ethylacrylate, propyl acrylate, methyl propyl acrylate, butyl acrylate, methyl butylacrylate, vinyl chloride, acrolein, (2-hydroxyl)ethylacrylate, styrene, 2-vinylpyridine, vinylpyrrolidone, caprolactam, adipic acid and hexadiamine. The modified protein macromolecules also may be prepared by a condensation reaction of polyamide and the protein macromolecules including casein, gelatin, and fur-protein.
The reactive groups of the dyes, which can react with the amino groups of the modified protein macromolecules, have the structure 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K. 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
(3) xe2x80x94SO2CH2CH2Y3xe2x80x83xe2x80x83(F3)
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
(4) xe2x80x94SO2NHCH2CH2Y3xe2x80x83xe2x80x83(F4)
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K. 
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X, or xe2x80x94N(CH3)CH2CH2SO3X; R is xe2x80x94H, xe2x80x94CH3, or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
(6) xe2x80x94NHCOCY4xe2x95x90CHY5xe2x80x83xe2x80x83(F6)
wherein Y4 is xe2x80x94H, or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl, or xe2x80x94Br.
(7) xe2x80x94NHCOCHY4CH2Y6xe2x80x83xe2x80x83(F7)
wherein Y4 is xe2x80x94H, or xe2x80x94Br; Y6 is xe2x80x94Br, or xe2x80x94OSO3X; X is xe2x80x94H, xe2x80x94Na, or xe2x80x94K.
In the present invention, the parent dyes are the azo dyes, azo metal complex dyes and anthraquinone dyes which can react with the amino groups of the protein macromolecules or modified protein macromolecules.
The azo dyes have three kinds of structures(D1, D2, D3) 
wherein R1, R4 and R8 each represents xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94OH, xe2x80x94COOX or xe2x80x94SO3X respectively; R5 is xe2x80x94H, xe2x80x94CH3, xe2x80x94COOX, xe2x80x94SO3X, xe2x80x94SO2NH2, or 
R2, R3, R6 and R7 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94OCH3, xe2x80x94NO2, xe2x80x94SO2NHR, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(C2H4OH)2, xe2x80x94N(CH2OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K. 
wherein R4, R7 and R8 each represents xe2x80x94H, xe2x80x94CH3, xe2x80x94OH, xe2x80x94OCH3, xe2x80x94NO2, xe2x80x94SO3X, or xe2x80x94COOX respectively; R1, R2, R3, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OR, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NO2, xe2x80x94N(R)2, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, xe2x80x94N(R)2, xe2x80x94(CH2OH)2, xe2x80x94SO2R, xe2x80x94N(C2H4OH)2, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K. 
wherein R3 is xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94OH, xe2x80x94COOX, xe2x80x94SO3X, xe2x80x94SO2NH2 or xe2x80x94NHCOCH3; R1, R2, R4 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OR, xe2x80x94NO2, xe2x80x94N(R)2, xe2x80x94NHCOCH3, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The azo metal complex dyes have four kinds of structures (D4, D5, D6, D7) 
wherein Me is Cu, Co, Ni and Cr; R1, R2, R3, R4, R5 and R6 each represents respectively xe2x80x94H, xe2x80x94Cl, xe2x80x94CH3, xe2x80x94OCH3, xe2x80x94SO3X, xe2x80x94COOX, xe2x80x94CH2SO3X, xe2x80x94NH2, xe2x80x94N(CH3)2, xe2x80x94NHCOCH3, xe2x80x94NHCONH2, 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
The anthraquinone dyes have one kind of structure (D8) 
wherein m or n is 0 or 1 respectively; L is 0, 1, 2, or 3; J is xe2x80x94CH3, xe2x80x94Cl, xe2x80x94SO3X; G is 
xe2x80x94SO2CH2CH2Y3, 
xe2x80x94SO2NHCH2CH2Y3, xe2x80x94NHCOCY4xe2x95x90CHY5, or xe2x80x94NHCOCHY4CH2Y6; wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
In the present invention, the preparation method of the protein macromolecular dyes can be divided into several groups according to the reactive groups of the dyes, which can react with the amino groups of the protein macromolecules.
(1) When the reactive group of the parent dyes is halotriazinyl: 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; the protein macromolecular dyes can be prepared as follows:
(a) When Y1 is xe2x80x94Cl or xe2x80x94F, Y2 is xe2x80x94Cl or xe2x80x94F: the protein macromolecular or modified protein macromolecular dyes can be obtained by the following reaction. A mixture of 1000 parts by weight protein macromolecules or modified protein macromolecules, 1000xcx9c200000 parts by weight H2O and 100xcx9c2000 parts by weight dyes with halotriazinyl reactive groups, which include azo dyes, azometal dyes and anthraquinone dyes, is heated to 30xcx9c85xc2x0 C. in pH 2xcx9c12 for 1xcx9c10 hours. 100xcx9c1000 parts by weight dyes, 5000xcx9c200000 parts by weight H2O, the range of 35xcx9c70xc2x0 C. and pH 3xcx9c10 are preferred. The pH is adjusted with acid or base which may be any one of H3CCOONa, ClH2CCOONa, Cl2HCCOONa, Cl3CCOONa, Na2CO3, NaHCO3, NaOH, Na2B4O7.10H2O, NaH2PO4 and Na2HPO4.
(b) When Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Y2 is xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, 
R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; the protein macromolecular dyes can be prepared as follows:
A mixture of 1000 part in weight protein macromolecules or modified protein macromolecules, 1000xcx9c200000 part in weight H2O and 100xcx9c2000 part in weight dyes with halotriazinyl reactive groups, which include azo dyes, azometal dyes and anthraquinone dyes, is heated to 30xcx9c85xc2x0 C. in pH 2xcx9c12 for 1xcx9c10 hours. 100xcx9c1000 parts by weight dyes, 5000xcx9c200000 parts by weight H2O, the range of 60xcx9c85xc2x0 C. and pH 3xcx9c10 are preferred. The pH is adjusted with acid or base which may be any one of H3CCOONa, ClH2CCOONa, Cl2HCCOONa, Cl3CCOONa, Na2CO3, NaHCO3, NaOH, Na2B4O710H2O, NaH2PO4 and Na2HPO4.
(2) When the reactive groups of the parent dyes are halopyrimidinyl: 
wherein Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94CH3; Y2 is xe2x80x94Cl, xe2x80x94F, xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K.
(a) when Y1 is xe2x80x94Cl or xe2x80x94F, Y2 is xe2x80x94Cl or xe2x80x94F: the protein macromolecular or modified protein macromolecular dyes can be obtained by the following reaction. A mixture of 1000 parts by weight protein macromolecules or modified protein macromolecules, 1000xcx9c200000 parts by weight H2O and 100xcx9c2000 parts by weight dyes with halotriazinyl reactive groups, which include azo dyes, azometal dyes and anthraquinone dyes, is heated to 30xcx9c85xc2x0 C. in pH 2xcx9c12 for 1xcx9c10 hours. 100xcx9c1000 parts by weight dyes, 5000xcx9c200000 parts by weight H2O, the range of 35xcx9c70xc2x0 C. and pH 3xcx9c10 are preferred. The pH is adjusted with acid or base which may be any one of H3CCOONa, ClH2CCOONa, Cl2HCCOONa, Cl3CCOONa, Na2CO3, NaHCO3, NaOH, Na2B4O7 10H2O, NaH2PO4, Na2HPO4.
(b) When Y1 is xe2x80x94Cl, xe2x80x94F or xe2x80x94CH3; Q is xe2x80x94Cl, xe2x80x94F, xe2x80x94CH3; Y2 is xe2x80x94R, xe2x80x94OR, xe2x80x94NHCH2SO3X, 
xe2x80x94N(R)2, xe2x80x94N(CH2OH)2, xe2x80x94N(C2H4OH)2, xe2x80x94SO2R, R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K, the protein macromolecular dyes can be prepared as follows:
A mixture of 1000 parts by weight protein macromolecules or modified protein macromolecules, 1000xcx9c200000 parts by weight H2O and 100xcx9c2000 parts by weight dyes with halotriazinyl reactive groups, which include azo dyes, azo metal dyes and anthraquinone dyes, is heated to 30xcx9c85xc2x0 C. in pH 2xcx9c12 for 1xcx9c10 hours. 100xcx9c1000 parts by weight dyes, 5000xcx9c200000 parts by weight H2O, the range of 60xcx9c85xc2x0 C. and pH 3xcx9c10 are preferred. The pH is adjusted with acid or base which may be any one of H3CCOONa, ClH2CCOONa, Cl2HCCOONa, Cl3CCOONa, Na2CO3, NaHCO3, NaOH, Na2B4O7 10H2O, NaH2PO4, Na2HPO4.
(3) When the reactive groups of the parent dyes are expressed as follows: 
wherein Y3 is xe2x80x94Cl, xe2x80x94OSO3X or xe2x80x94N(CH3)CH2CH2SO3X; Y4 is xe2x80x94H or xe2x80x94Br; Y5 is xe2x80x94H, xe2x80x94Cl or xe2x80x94Br; Y6 is xe2x80x94Br or xe2x80x94OSO3X; R is xe2x80x94H, xe2x80x94CH3 or xe2x80x94C2H5; X is xe2x80x94H, xe2x80x94Na or xe2x80x94K; the protein macromolecular dyes can be prepared as follows:
A mixture of 1000 parts by weight protein macromolecules or modified protein macromolecules, 1000xcx9c200000 parts by weight H2O and 100xcx9c2000 parts by weight dyes with halotriazinyl reactive groups, which include azo dyes, azo metal dyes and anthraquinone dyes, is heated to 30xcx9c85xc2x0 C. in pH 2xcx9c12 for 1xcx9c10 hours. 100xcx9c1000 parts by weight dyes, 5000xcx9c200000 parts by weight H2O, the range of 50xcx9c80xc2x0 C. and pH 3xcx9c10 are preferred. The pH is adjusted with acid or base which may be any one of H3CCOONa, ClH2CCOONa, Cl2HCCOONa, Cl3CCOONa, Na2CO3, NaHCO3, NaOH, Na2B4O7 10H2O, NaH2PO4, Na2HPO4.
The protein macromolecular dyes may be used in dyeing protein materials such as leather, silk and wool.
In general, leather is first dyed by acid dyes, direct dyes or reactive dyes, then coated by a coating agent. When acid dyes or direct dye is used in dyeing leather, the fastness is usually 3xcx9c4 grade. And reactive dye is not friendly to the environment because of the low reactivity of the dye. During the finishing process, membrane-forming agent, pigment paste and other additives are often necessary in the coating agent after the leather is dyed.
The present invention provides the protein macromolecular dyes of good properties. Because abundant parent dyes are linked to protein macromolecular support matrix, the dyes not only have bright color like acid dyes, direct dyes and reactive dyes, but also increased color brightness. The fastness thereof is higher than that of acid and direct dyes because the macromolecules may be crosslinked by crosslinking agents. The fixation of the protein macromolecular dyes in dyeing leather is much higher than that of conventional acid dyes, direct dyes and reactive dyes because the structure of the protein macromolecular dyes is similar to protein material such as leather. Therefore, the dyeing process in which the protein macromolecular dyes are used on the leather has very low environmental pollution. The protein macromolecular dyes are of compatibility, ability of filling and membrane-forming the common properties of macromolecular material. So they can be used in protein material staining as novel dyes which can complete dyeing, coating and membrane-forming in one step.
The conversion of the dyes is above 90% in the present, process for preparing protein macromolecule because the chemical reaction of dyes with protein macromolecule or modified protein macromolecule is performed in homogeneous solution, and it can be above 95% by changing the ratio of the dyes to protein macromolecule in accordance with the structures of the dyes. The content of the parent dyes on the macromolecule support matrix (in weight) is above 20%, and it can be 50% by changing the ratio of the dyes to protein macromolecule. The obtained macromolecular dyes can be formulated into products in different amount.
During the dyeing process, the protein macromolecular dyes are absorbed on the surface of leather, diffused to the inner part and crosslinked by using crosslinking agent so as to be fastened.
The protein macromolecular dyes have bright colors like acid dyes, direct dyes and reactive dyes. Their fixation is above 95% when they are applied in dyeing leather. The dry and wet fastness of the leather dyed by the protein macromolecular dyes are 5 and 4xcx9c5 degree respectively. It is also the same after coating.
Besides the dyeing ability, the protein macromolecular dyes also have filling ability to improve fullness and sponginess of leather. The dyeing and finishing process of the protein macromolecular dyes on leather is convenient under mild reaction conditions.
The protein macromolecular dyes may be used on other protein materials like silk and wool with excellent dyeing result and fastness.